Delaying the gelation of water soluble polymers

ABSTRACT

A process is disclosed for delaying the rate at which water soluble polymers are gelled by an aldehyde and a phenolic compound and for increasing the mechanical strength of these gels which comprises contacting an aqueous solution of said water soluble polymer, aldehyde, phenolic compound, and water with from 0.004 to about 0.049 wt % of a transition metal ion. In addition, novel gelable compositions are disclosed.

This application is a division of application Ser. No. 010,507, filedFeb. 3, 1987, now U.S. Pat. No. 4,822,842.

The present invention relates to a process for delaying the rate atwhich water soluble polymers are gelled by organic crosslinking agents.Another aspect of the invention relates to a process for increasing themechanical strength of gelled water soluble polymers. A further aspectof the invention relates to novel compositions of gelable water solublepolymers.

It is well known to those skilled in the art that gelled water solublepolymers are useful in enhanced oil recovery operations. They have beenused to alter the permeability of underground formations in order toenhance the effectiveness of water flooding operations.

The polymers, along with an appropriate crosslinking agent are injectedin an aqueous solution into the formation. They percolate into and gelin the regions having the highest water permeability. Any fluidsinjected into the formation in subsequent flooding operations, will thenbe diverted away from the gels into regions of the formation having alower water permeability.

Although this technique is effective in enhancing hydrocarbonproduction, it does have problems. The primary one being that the watersoluble polymers gel fairly quickly after being injected into theformation. Quite often only the regions near the well bore are treated,since the polymers gel before they have an opportunity to permeatethroughout the entire formation.

Numerous attempts have been made to delay the rate at which thesepolymers gel. Thus, Hessert et al in U.S. Pat. No. 3,926,258, assignedto Phillips Petroleum Company, disclose a method for delaying the rateof which such water soluble polymers are gelled by use of inorganiccrosslinking agents.

Although a method has been discovered for delaying the rate at whichinorganic crosslinking agents gel water soluble polymers, a method fordelaying the effects of organic crosslinking agents has not beendiscovered.

Another problem associated with treating underground formations withgelled water soluble polymers, is the duration of the plug created bythe gel and the corresponding increase in hydrocarbon production. Thesegelled polymer plugs are exposed to numerous mechanical forces withinthe formation which tend to promote the breakdown of the plug. When theplug breaks down, hydrocarbon production decreases, which necessitatesretreating the formation with more water soluble polymers.

Thus, it would be a valuable contribution to the art to have a processwhich would delay the rate at which organic crosslinking agents effectthe gelatin of water soluble polymers.

It would also be a valuable contribution to the art to have a processwhich would increase the mechanical strength of water soluble polymerswhich are gelled by organic crosslinking agents.

It is thus an object of the present invention to provide a process fordelaying the rate at which water soluble polymers are gelled by organiccrosslinking agents.

It is a further object of the present invention to provide a process forincreasing the mechanical strength of water soluble polymers which havebeen gelled by organic crosslinking agents.

It is yet another object of the present invention to provide novelcompositions of water soluble polymers which have a delayed rate ofgelation.

Other aspects and objects of this invention will become apparenthereinafter as the invention is more fully described in the followingdisclosure and appended claims.

In accordance with the present invention, it has been discovered thatthe rate at which water soluble polymers are gelled by organiccrosslinking agents can be delayed, when the water soluble polymer andthe organic crosslinking agent are contacted with less than 0.05 wt % ofa metal ion in an aqueous environment.

Further, in accordance with the present invention it has been discoveredthat gels of water soluble polymers which have been gelled in an aqueousenvironment by an organic crosslinking agent in the presence of lessthan 0.05 wt % of a metal ion, have improved mechanical strength.

Further, in accordance with the present invention there is providednovel gelable compositions comprising water soluble polymers, water, anorganic crosslinker, and a metal ion which has a delayed rate ofgelation and improved mechanical strength within a formation.

As used in this application, the term water soluble polymer or polymerrefers to those polymers which are truly water soluble or those whichare dispersible in water or other aqueous medium to form a stablecolloidal suspension which can be pumped into a formation and gelledtherein.

The water soluble polymers which are suitable for use in the presentinvention include those which contain from 5 to 100 mole percent of atleast one monomer of the formula ##STR1## wherein R₁, R₂, and R³ areselected from the group consisting of hydrogen or alkyl groupscontaining from 1 to 3 carbon atoms, of which acrylamide andmethacrylamide are the preferred examples; and from 0 to 95 mole percentof at least one monomer selected from the group consisting of;

(A) those monomers represented by the formula: ##STR2## wherein R isselected from the group consisting of hydrogen or alkyl radicalscontaining from 1 to 6 carbon atoms, R' is selected from the groupconsisting of alkylene radicals containing from 1 to 6 carbon atoms oran arylene radical containing from 6 to 10 carbon atoms, and M isselected from the group consisting of hydrogen, ammonium, potassium, orsodium, of which 2-acrylamido-2-methylpropane sulfonic acid or sodium2-acrylamido-2-methylpropane sulfonate are the preferred examples; or

(B) monomers represented by the formula ##STR3## where R₁, R₂ and R₃ areindependently selected from the group consisting of hydrogen or alkylradicals containing from 1 to 2 carbon atoms of whichN-vinyl-2-pyrrolidone is the preferred example; or

(C) at least one monomer selected from the group consisting of acrylicacid, methacrylic acid, vinylsulfonic acid, vinylbenzylsulfonic acid,vinyl acetate, acrylonitrile, methyl acrylonitrile, vinyl alkyl ether,vinyl chloride, maleic anhydride, vinyl substituted cationic quaternaryammonium compounds, (acryloyloxy-ethyl)diethylmethylammonium methylsulfide, sodium acrylate; or

(D) mixtures thereof.

The polymerization of any of the above-described monomers and theirresulting polymers are well known to those skilled in the art. There arenumerous references which disclose methods of polymerizing thesemonomers. For example, see U.S. Pat. No. 4,244,826 or European patentapplication No. 0115836.

The manner in which these monomers are polymerized into water solublepolymers or the resulting polymer is not critical to the practice of thepresent invention.

The molecular weight of the water soluble polymers utilized in thepresent invention is not critical. It is presently preferred, however,that the polymer have a molecular weight of at least about 100,000 andmore preferably 100,000 to 20,000,000. The upper limit is not criticalas long as the polymer is still water dispersible and can be pumped intothe formation.

The presently preferred class of water soluble polymers are thoseselected from the group consisting of homopolymers of acrylamide,homopolymers of methacrylamide, copolymers of acrylamide and sodiumacrylate, copolymers of acrylamide and sodium2-acrylamido-2-methylpropane sulfonate, copolymers of acrylamide andN-vinyl-2-pyrrolidone, and terpolymers of acrylamide,N-vinyl-2-pyrrolidone, and sodium 2-acrylamido-2-methylpropanesulfonate. The ratio of the monomers in the above-described polymers isnot critical; provided however, that at least 5 mole % of acrylamide ispresent in the above-described polymers.

The organic crosslinking agents of the present invention are formedfrom: (A) a water dispersible aldehyde, and (B) a phenolic compound.

As a general guide, the amount of aldehyde used in preparing the gelledcompositions of the invention will be in the range of from about 0.03 to1.2 wt %, preferably from 0.04 to about 1 wt % based on the total weightof the composition. The amount of phenolic compound used will be in therange of from about 0.01 to 2 wt %, preferably from about 0.04 to about1 wt % based on the total weight of the composition. The molar ratio ofaldehyde to phenolic compound will be in the broad range of from about0.1:1 to 25:1, with a preferred range of from 0.5:1 to 6:1, morepreferably from about 1:1 to 4:1.

Any water dispersible aldehyde can be utilized in the practice of thepresent invention. Thus, suitable aldehydes can be selected from thegroup consisting of aliphatic monoaldehydes, aromatic monoaldehydes,aliphatic dialdehydes, and aromatic dialdehydes. Preferred aldehydes canbe selected from the group consisting of formaldehyde, paraformaldehyde,acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde,valeraldehyde, heptaldehyde, decanal, glyoxal; glutaradehyde,terephthaldehyde, or mixtures thereof.

As used in this application, the term phenolic compound refers tocompounds represented by the formula: ##STR4## wherein R₁, R₂, R₃, R₄and R₅ are independently selected from the group consisting of hydroxylgroups, amines containing from 0 to 6 carbon atoms, alkoxy groupscontaining from 1 to 6 carbon atoms; NHCOCH₃, alkyl groups containingfrom 1 to 6 carbon atoms, a phenyl group, NO₂, COOH, COH, sulfonicacids, ketones containing from 1 to 6 carbon atoms, F, Cl, Br, I andhydrogen; provided that at least 2 of the above R groups are hydrogenand the resulting compound is water dispersible.

Another group of compounds included within the term phenolic compoundare the flavotannins. Flavotannins are polyphenolic materials which areextracted from the bark and wood of trees. Querbracho is an example of asuitable flavotannin.

Representative examples of suitable phenolic compounds can be selectedfrom the group consisting of monohydroxy phenols, polyhydroxy phenols,monohydroxy napthols, polyhydroxy naphthols, o-cresol, m-cresol,p-cresol, o-fluorophenol, m-fluorophenol, p-fluorophenol,o-chlorophenol, m-chlorophenol, p-chlorophenol, o-bromophenol,m-bromophenol, p-bromophenol, o-iodophenol, m-iodophenol, p-iodophenol,o-nitrophenol, m-nitrophenol, p-nitrophenol, flavotannins, phenol,resorcinol, catechol, hydroquinone, phloroglucinol, pyrogallol,1,3-dihydroxynaphthalene, o-aminophenol, p-aminophenol, m-aminophenol,o-methylaminophenol, p-methylaminophenol, m-methylaminophenol,o-methoxyphenol, p-methoxyphenol, m-methoxyphenol, o-N-acetamidophenol,p-N-acetamidophenol, m-N-acetamidophenol, o-hydroxybenzoic acid,p-hydroxybenzoic acid, m-hydroxybenzoic acid, o-phenolsulfonic acid,p-phenosulfonic acid, m-phenolsulfonic acid, dichlorophenols,4,4-biphenol or mixtures thereof.

Presently preferred phenolic compounds are those selected from the groupconsisting of phenol, resorcinol, catechol, hydroquinone,phloroglucinol, pyrogallol, 4,4'-biphenol, 1,3-dihydroxynaphthalene, ormixtures thereof.

The key to the practice of the present invention is to effect gelling ofthe water soluble polymer in the presence of the metal ion. The metalion delays the rate at which the aldehyde and the phenolic compoundcrosslink the composition to form a gel of the water soluble polymer. Inaddition, the presence of the metal ion also serves to produce astronger gel.

Suitable metal ions for the practice of the present invention can beselected from the group consisting of Fe⁺³, Fe⁺², Cu⁺², Co⁺³, Ni⁺²,Sn⁺⁴, Ti⁺⁴, Zn⁺², V⁺³, and Zr⁺⁴.

The anion associated with the metal ion is not critical to the practiceof the present invention, provided that the resulting compound is watersoluble. Thus, suitable anions associated with the metal ion can beselected from the group consisting of chlorides, bromides, iodides,fluorides, sulfates, nitrates, phosphates and carboxylates of from 1 to4 carbon atoms.

The constituents of the present invention should be present in thefollowing quantities:

    ______________________________________                                                       Broad      Preferred                                                          Range Wt % Range Wt %                                          ______________________________________                                        water soluble polymers                                                                         0.1-5        0.3-2                                           aldehyde         .03-1.2      0.04-1                                          phenolic compound                                                                              .01-2        .04-1                                           metal ion        .004-about 0.049                                                                           .008-.03                                        water            92-99.9      96-99.6                                         ______________________________________                                    

It is critical that the concentration of metal ion be kept below 0.05weight percent. Concentrations above 0.05 weight percent promoteovercrosslinking and result in syneresis of the gel.

The delay in crosslinking is accomplished by merely incorporating anappropriate metal ion onto an aqueous solution containing water solublepolymer, aldehyde, phenolic compound and water. The order in which theconstituents are mixed is not critical to the practice of the presentinvention, however, the metal ion must be added before the aldehyde andphenolic crosslinking agent has had an opportunity to gel the watersoluble polymer.

The use of gelled polymers to alter the water permeability ofunderground formations is well known to those skilled in the art.Generally, an aqueous solution containing the polymer and a crosslinkingagent is pumped into the formation so that it can diffuse into the morewater soluble portions of the formation and alter that waterpermeability by gelling therein.

The present invention can be used in a similar manner. An aqueoussolution containing the water soluble polymer, aldehyde, phenoliccompound, and metal ion is pumped into the formation so that it altersthe water permeability of the formation in a similar manner whengelation takes place. The present invention's advantage lies in the factthat since the gelation of the polymer is delayed, the polymer has anopportunity to travel farther into the formation and effect the waterpermeability of portions of the formation that would normally gountreated due to their distance from the injection site. In addition,the resulting gel exhibits improved strength.

The nature of the underground formation treated is not critical to thepractice of the present invention. The metal ion will delay the gelationof the water soluble polymers in fresh water, salt water, or brines, aswell as at a temperature range of from 70° F. to 400° F.

The following specific examples are intended to illustrate theadvantages of this invention, but are not intended to unduly limit thisinvention.

EXAMPLE I

The purpose of this example is to demonstrate how the incorporation of ametal ion, into a solution of water soluble polymers will delay the rateat which the polymer is gelled by an aldehyde and a phenolic compound.

A one percent solution of a terpolymer composed of 30 wt % ofN-vinyl-2-pyrrolidone, 15 wt % of acrylamide, and 55 wt % of sodium2-acrylamindo-2-methylpropane sulfonate was prepared in the followingmanner. 16.66 grams of an inverse emulsion which contained 32.4% of theabove-described active terpolymer was mixed with 483.34 ml of syntheticsea water.

The synthetic sea water used had the following formula:

    ______________________________________                                        NaHCO.sub.3         3.69 grams                                                Na.sub.2 SO.sub.4   77.19 grams                                               NaCl                429.00 grams                                              CaCl.sub.2.2H.sub. 2 O                                                                            29.58 grams                                               MgCl.sub.2 .6H.sub.2 O                                                                            193.92 grams                                              distilled H.sub.2 O q.s. to 18 liters                                         ______________________________________                                    

A solution containing 26 weight percent of phenol and 26 weight percentof formaldehyde was prepared by mixing 12.1 cc of a solution containing88 weight percent phenol with 27.9 cc of a solution containing 37percent formaldehyde.

A solution containing 1 weight percent of ferric ion was prepared bymixing 4.827 grams of FeCl₃.6H₂ O was sufficient distilled water to form100 ml of solution.

20 cc of the solution, containing 1 percent of the terpolymer was placedin a 2.3 cm×22.5 cm long ampule. 0.076 ml of the solution containingphenol and formaldehyde was also placed in the ampule.

Four other identical ampules were prepared in an identical manner exceptthat varying quantities of ferric ion were added to the ampules.

The five ampules were sealed under nitrogen and then placed in an ovenand heated to 250° F. Periodically, the ampules were removed from theoven and it was visually determined whether the polymers had formed agel.

The following results were obtained.

                  TABLE I                                                         ______________________________________                                                                            Gelation                                  Ampule #  Iron Conc (ppm)                                                                            Iron Conc (wt %)                                                                           Period                                    ______________________________________                                        1         0            0            1.8 days                                  2         40           0.004        13 days                                   3         80           0.008        16 days                                   4         120          0.012        13 days                                   5         200          0.020        13 days                                   ______________________________________                                    

The above data demonstrates that the incorporation of a transition metalion into a solution of water soluble polymers delays the rate at whichthe polymer is gelled by an aldehyde and a phenolic compound.

EXAMPLE II

The purpose of this example is to demonstrate that gelling water solublepolymers in the presence of a metal ion increases the mechanicalstrength of the gel.

The five ampules of the previous example were aged in a 250° F. oven for34 days. At the end of the 34 days, they were removed from the oven, andthe mechanical strength of the gel was determined.

This was determined in the following manner. The ampule was laidhorizontally along a graduated scale and the spreading of the gel wasmeasured. If the gel was weak, then it would spread along the entirelength of the tube. Likewise, as the strength of the gel increased, thedistance the gel spread decreased.

This relationship can be expressed mathematically as (A1-T1)×100/A1;where A1 equals the ampule length, T1 equals the tongue length of thegel measured in centimeters from the point at which the gel contacts theentire circumference of the tube to the farthest point that the gel hasspread. Thus, the strongest gels would have a gel strength of 100%,whereas the weakest gels would have a gel strength of 0.

The following results were obtained.

                  TABLE II                                                        ______________________________________                                                Iron Conc Iron Conc Tongue                                            Ampule #                                                                              (in ppm)  (wt %)    Length Gel Strength %                             ______________________________________                                        1       0         0         1.2    94                                         2       40        0.004     0.3    98                                         3       80        0.008     0.2    99                                         4       120       0.012     0.0    100                                        5       200       0.020     0.0    100                                        ______________________________________                                    

The above data demonstrates that gelling water soluble polymers in thepresence of a metal ion increases the mechanical strength of the gel.

EXAMPLE III

The purpose of this example is to demonstrate that other metal ionsbesides iron, will delay the rate at which water soluble polymers aregelled by an aldehyde and a phenolic compound.

One ampule containing no transition metal ions was prepared in a manneridentical to that in Example I. Six other ampules were also prepared inan identical manner to those in Example I except that other metals wereadded to the tube to the ampules rather than iron.

The following results were obtained.

                  TABLE III                                                       ______________________________________                                                Metal   Conc of Metal                                                                             Conc of Metal                                                                           Gelation                                Ampule #                                                                              Ion     Ion in ppm  Ion in wt %                                                                             Period                                  ______________________________________                                        1       None    --          0         18.7 hrs.                               2       Fe.sup.+2                                                                             150         0.15      7.8 days                                3       Zn.sup.+2                                                                             150         0.15      2.8 days                                4       Ni.sup.+2                                                                             150         0.15      19 days                                 5       Cu.sup.+2                                                                             150         0.15      7.8 days                                6       Zr.sup.+4                                                                             150         0.15      2.8 days                                ______________________________________                                    

The above data shows that these other metal ions also delay the rate atwhich water soluble polymers are gelled by aldehydes and phenoliccompounds.

EXAMPLE IV

The purpose of this example is to demonstrate that other transitionmetal ions will also increase the strength of water soluble polymergels.

The ampules prepared in Example III were aged for 65 days in a 250° F.oven. At the end of this period, they were removed from the oven and themechanical strength of the gels were determined in a manner identical tothat in Example II. The following results were obtained.

                  TABLE IV                                                        ______________________________________                                                                 Conc of                                                             Conc of   Metal                                                       Metal   Metal     Ion in  Tongue Gel                                   Ampule Ion     Ion in ppm                                                                              wt %    Length Strength                              ______________________________________                                        1      None    0         0       10.3   54                                    2      Fe.sup.+2                                                                             150       0.15    0      100                                   3      Zn.sup.+2                                                                             150       0.15    3.0    85                                    4      Ni.sup.+2                                                                             150       0.15    0      100                                   5      Cu.sup.+2                                                                             150       0.15    0.7    96                                    6      Zr.sup.+4                                                                             150       0.15    0      100                                   ______________________________________                                    

The above data demonstrates that zinc, nickel, cobalt, copper, andzirconium will also increase the strength of water soluble polymer gels.

EXAMPLE V

The purpose of this example is to demonstrate that a metal ion will alsodelay the rate at which a water soluble copolymer composed of acrylamideand N-vinyl-2-pyrrolidone is gelled by an aldehyde and a phenoliccompound.

A 0.5 weight percent solution of a copolymer composed of 50 wt %acrylamide and 50 wt % of N-vinyl-2-pyrrolidone was prepared in thefollowing manner. 16.67 grams of a gel-log, containing 30 wt % of theabove-described copolymer was dissolved in 983.33 grams of water. Thesolution was stirred overnight to insure total hydration of the polymer.

A solution containing 3.3 wt % of a ferric ion was prepared by mixing8.0 grams of FeCl₃.6H₂ O with 50 ml of water.

A solution containing 26 wt % of phenol and 26 wt % of formaldehyde wasprepared in a manner identical to that in Example I.

The solution containing the copolymer was sub-divided into five separate200 ml samples.

Varying quantities of the phenol-formaldehyde solution was added to fourof the above-described 200 ml samples of copolymer.

Four test samples were prepared by placing 20 cc from each of the abovepolymer-phenol-formaldehyde solutions into separate 2.3 cm×22.5 cm longampules.

Four more identical test samples were prepared, except that 0.125 ml ofthe ferric ion solution were placed in each ampule resulting in a finalconcentrate of 0.02 wt % iron.

The eight ampules were sealed under nitrogen and then placed in an ovenand heated to 200° F. Periodically, the ampules were removed from theoven and it was visually determined whether the polymers had formed agel.

The following results were obtained.

                  TABLE V                                                         ______________________________________                                                Iron                                                                          Conc     Phenol     Formaldehyde                                                                            Gelation                                Ampule #                                                                              (wt %)   Conc (wt %)                                                                              Conc (wt %)                                                                             Period                                  ______________________________________                                        1       0        0.05       0.05      7 days                                  2       0        0.1        0.1       7 days                                  3       0        0.25       0.25      2 days                                  4       0        0.50       0.5       1 day                                   5       0.02     0.05       0.05      96 days                                 6       0.02     0.1        0.1       96 days                                 7       0.02     0.25       0.25      25 days                                 8       0.02     0.5        0.5       2 days                                  ______________________________________                                    

The above data demonstrates that a metal ion will delay the rate atwhich an aldehyde and a phenolic compound will gel the water solublepolymers of the present invention.

Reasonable variations can be made in view of the following disclosurewithout departing from the spirit and scope of the invention.

What is claimed is:
 1. In an enhanced oil recovery process wherein thewater permeability of selected portions of an underground formation isdecreased by injecting a gelable composition containing;from 0.1-5 wt %of a water soluble polymer wherein said water soluble polymer containsfrom 5 to 100 mole percent of a monomer selected from those monomersrepresented by the following formula ##STR5## wherein R₁, R₂, and R₃ areselected from the group consisting of hydrogen of alkyl groupscontaining from 1 to 3 carbon atoms; and from 0 to 95 mole percent of amonomer selected from the group consisting of;(A) those monomers whichcan be represented by the formula ##STR6## wherein R is selected fromthe group consisting of hydrogen or alkyl radicals containing from 1 to6 carbon atoms, R' is selected from the group consisting of alkyleneradicals containing from 1 to 6 carbon atoms or an arylene radicalcontaining from 6 to 10 carbon atoms, and M is selected from the groupconsisting of hydrogen, ammonium, potassium, or sodium, (B) thosemonomers represented by the following formula, ##STR7## where R₁, R₂ andR₃ are independently selected from the group consisting of hydrogen oralkyl radicals containing from 1 to 2 carbon atoms; and (C) thosemonomers selected from the group consisting of acrylic acid, methacrylicacid, vinylsulfonic acid, vinylbenzylsulfonic acid, vinylbenzenesulfonicacid, vinyl acetate, arylonitrile, methyl acrylonitrile, vinyl alkylether, vinyl chloride, maleic anhydride, vinyl substituted cationicquaternary ammonium compounds (acryloyloxyethyl)dimethylmethylammoniummethyl sulfate, sodium acrylate; and (D) mixtures thereof;from 0.03-1.2wt % of a water dispersible aldehyde; from 0.01-2 wt % of a phenoliccompound; and from 92-99.9 wt % of water; the improvement whichcomprises: pumping into an underground formation, prior to gelling, saidgelable composition containing said water soluble polymer, said waterdispersible aldehyde, said phenolic compound, water, and a metal ionselected from the group consisting of Fe²⁺, Fe³⁺, Cu²⁺, Co³⁺, Ni²⁺,Sn⁴⁺, Ti⁴⁺, Zn²⁺, V₃₊, and Zr⁴⁺, wherein said metal ion is present in anamount sufficient to delay the gelling of said gelable composition, in amanner which facilitates the contacting of said water soluble polymer,said water dispersible aldehyde, said phenolic compound, water, and saidmetal ion thereby delaying the gelling of said gelable composition. 2.The process of claim 1 whereinsaid water soluble polymer is selectedfrom the group consisting of homopolymers of acrylamide, homopolymers ofmethacrylamide, copolymers of acrylamide and acrylic acid, copolymers ofacrylamide and sodium acrylate, copolymers of acrylamide and sodiumacrylate, copolymers of acrylamide and N-vinyl-2-pyrrolidone, copolymersof acrylamide and sodium 2-acrylamido-2-methylpropane sulfonate, andterpolymers of N-vinyl-2-pyrrolidone, acrylamide, and sodium2-acrylamido-2-methylpropane sulfonate;said aldehyde is selected fromthe group consisting of formaldehyde, paraformaldehyde, acetaldehyde,propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde,heptaldehyde, decanal, glyoxal, glutaraldehyde, terephthaldehyde, ormixtures thereof; and said phenolic compound is selected from the groupconsisting of those phenols represented by the formula: ##STR8## whereinR₁, R₂, R₃, R₄ and R₅ are independently selected from the groupconsisting of hydroxyl groups, amines containing from 0 to 6 carbonatoms, alkoxy groups containing from 1 to 6 carbon atoms; NHCOCH₃, alkylgroups containing from 1 to 6 carbon atoms, a phenyl group, NO₂, COOH,COH, sulfonic acids, ketones containing from 1 to 6 carbon atoms, F, Cl,Br, I and hydrogen; provided that at least 2 of the above R groups arehydrogen and the resulting compound is water dispersible.
 3. The processof claim 1 wherein said phenolic compound is selected from the groupconsisting of phenol, resorcinol, catechol, hydroquinone,phloroglucinol, pyrogallol, 4,4-biphenol, 1,3-dihydroxynaphthalene, ormixtures thereof.
 4. The process of claim 1 whereinsaid water solublepolymer is present in the range of from 0.3-2 wt %; said waterdispersible aldehyde is present in the quantity of from 0.04-1 wt %;said phenolic compound is present in the quantity of from 0.04-1 wt %;said water is present in the quantity of from 96-99.6 wt %; and saidmetal ion is present in the quantity of from 0.008-0.03 wt %.
 5. Theprocess of claim 1 whereinsaid water soluble polymer is a terpolymer ofN-vinyl-2-pyrrolidone, acrylamide, and sodium2-acrylamido-2-methylpropane sulfonate; said water dispersible aldehydeis formaldehyde; said phenolic compound is phenol; and said metal ion isFe²⁺.
 6. The process of claim 1 whereinsaid water soluble polymer is aterpolymer of N-vinyl-2-pyrrolidone, acrylamide, and sodium2-acrylamido-2-methylpropane sulfonate; said water dispersible aldehydeis formaldehyde; said phenolic compound is phenol; and said metal ion isZn²⁺.
 7. The process of claim 1 whereinsaid water soluble polymer is aterpolymer of N-vinyl-2-pyrrolidone, acrylamide, and sodium2-acrylamido-2-methylpropane sulfonate; said water dispersible aldehydeis formaldehyde; said phenolic compound is phenol; and said metal ion isNi²⁺.
 8. The process of claim 1 whereinsaid water soluble polymer is aterpolymer of N-vinyl-2-pyrrolidone, acrylamide, and sodium2-acrylamido-2-methylpropane sulfonate; said water dispersible aldehydeis formaldehyde; said phenolic compound is phenol; and said metal ion isCu²⁺.
 9. The process of claim 1 whereinsaid water soluble polymer is aterpolymer of N-vinyl-2-pyrrolidone, acrylamide, and sodium2-acrylamido-2-methylpropane sulfonate; said water dispersible aldehydeis formaldehyde; said phenolic compound is phenol; and said metal ion isZr⁴⁺.
 10. The process of claim 1 whereinsaid water soluble polymer is acopolymer of N-vinyl-2-pyrrolidone and acrylamide; said waterdispersible aldehyde is formaldehyde; said phenolic compound is phenol;and said metal ion is Fe³⁺.